Reaction products of metal oxides and salts with phosphorus compounds

ABSTRACT

Reaction products are prepared from metal oxides and salts and phosphorus compounds containing trivalent phosphorus. The reaction products are useful as flame retardants and smoke suppressants.

CROSS REFERENCES TO RELATED APPLICATIONS

This is a division of application Ser. No. 898,590, filed Apr. 12, 1978,now U.S. Pat. No. 4,206,133, which is a divisional of Application Ser.No. 724,192 filed Sept. 17, 1976, now U.S. Pat. No. 4,133,823 issuedJan. 9, 1979; which is a continuation-in-part of Application Ser. No.553,947 filed Feb. 28, 1975, now abandoned, which is a continuation ofApplication Ser. No. 223,295 filed Feb. 3, 1972, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to complex reaction products of metal oxides andmetal salts with phosphorus compounds or mixture of same containing atleast some trivalent phosphorus, their method of preparation and theiruse as flame retardants and smoke suppressants in synthetic and naturalmaterials.

Heretofore, organometallic phosphorus compounds have been prepared byreacting various metal derivatives with phosphorus compounds. Thus, U.S.Pat. No. 2,228,653 discloses the preparation of organometal salts suchas calcium cetyl phosphate by the reaction of a metal carbide, i.e.,calcium carbide, and an organic phosphorus-containing acid. The organicacids disclosed as useful in the reaction include organic acidscontaining phosphorus in either the trivalent or pentavalent state. Noutility is disclosed for the compounds.

U.S. Pat. No. 2,329,707 discloses the preparation of aluminum, chromiumand tin salts of phosphorus acids containing pentavalent phosphorus byreacting the acid with an alkali metal hydroxide and then precipitatingthe desired metal salt from the solution of the alkaline salt byaddition of aluminum, chromium or tin ion. The compounds are disclosedas useful as antioxidants, lubricating and drying oils and varnishes.

U.S. Pat. No. 2,441,671 discloses foam inhibiting compounds which areGroup I metal salts of alkyl alkylene diphosphates containingpentavalent phosphorus.

U.S. Pat. No. 2,416,985 discloses Groups II, III, IV and VI metal saltsof oxyacids of phosphorus-containing pentavalent phosphorus asstabilizing agents for lubricating oils.

U.S. Pat. No. 2,784,206 discloses metallo-vinyl phosphonates asstabilizers for polymeric materials.

U.S. Pat. No. 3,397,216 discloses coordination complexes of the halidesof antimony, tin and titanium with pentavalent phosphorus compounds. Thecoordination complexes are disclosed as useful flame retardants forpolymeric systems.

SUMMARY OF THE INVENTION

In accordance with the present invention, certain metal oxides and saltsor salts of ammonia and silicon are reacted with one or more phosphoruscompounds characterized by the presence of at least some trivalentphosphorus and by the absence of active protons or ionic halogens. Thereaction products are extremely complex and are apparently composed of apartial metallic oxide or salt or ammonium or silicon salt of thephosphorus compound, a coordinate complex of the oxide or salt with thephosphorus compound and a partial solution of the oxide or salt in thephosphorus compound, such components being in dynamic equilibrium. Thereaction products are extremely stable and heat resistant.

The reaction products of the invention are prepared by the reaction ofmetal oxides or salts or ammonium or silicon salts with mixtures ofphosphorus compounds, at least one of which is characterized by thepresence of trivalent phosphorus, or by the reaction of such oxides orsalts with a phosphorus-containing compond characterized by the presenceof both trivalent and pentavalent phosphorus. It is to be understood,however, that the reaction products are so complex that a simpledefinitive statement as to their physical and chemical structure, as setforth above, is theoretical only. It is entirely possible that specificoxides or salts may form reaction products with trivalent phosphoruscompounds which may exist predominantly in one or more of theabove-described phases.

Since the reaction products of this invention are extremely stable andhighly heat resistant, their primary utility is as flame retardants andsmoke suppressants. The reaction products of the invention do, in fact,impart outstanding flame retardant and smoke suppressant characteristicsto a wide variety of materials. Additionally, however, amazingly variedapplications have been found for the reaction products of the presentinvention. Thus, the reaction products may be used as reactive modifiersfor epoxy resins, unsaturated polyesters and other polymeric materials,as adhesion promoters for asphalt-based rubber adhesives, as reactivemodifiers and tackifiers for elastomeric materials, as antioxidants andsequestrating agents, as reactive additives for phenolics, as pigmentsand coloring agents, as agents for the electroless deposition of metalson metals and non-metals, as the basic component of printed circuits andmetallic decorations, as an aluminum soldering flux, as corrosioninhibitors and rust removers, as stabilizers for vinyl resins, astackifiers in resin formulations, as blowing agent aides, as ignitionretarders, as adhesive agents for fusing plastisols to metal, asfungicides and insecticides and as heat absorbent coatings.

Accordingly, the objective of this invention is to provide novel,complex reaction products of metal oxides and salts or ammonium orsilicon salts and trivalent phosphorus-containing compounds, theirmethod of preparation and their use as flame retardants and smokesuppressants for natural and synthetic resins and resin plasticizers andmaterials prepared therefrom.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The objective of this invention is accomplished by reacting a metaloxide or salt or mixture thereof or ammonium or silicon salt withphosphorus compounds which contain reactant trivalent phosphorus butwhich, in order to avoid the formation of simple salts, do not containactive protons or ionically bound halogens.

The metal oxides and salts which are used to prepare the complexreaction products of this invention are the various salts of the GroupIA metals, i.e., lithium, sodium, potassium, rubidium, cesium andfrancium; the Group IB metals, i.e., copper, silver and gold; Group IIAmetals, i.e., magnesium, calcium, strontium and barium; the Group IIBmetals, i.e., zinc, cadmium and mercury; the Group IIIB metals, i.e.,aluminum, gallium and indium; the Group IVA metals, i.e., titanium,zirconium and hafnium; the Group IVB metals, i.e., germanium, tin andlead; the Group VA metals, i.e., vanadium, niobium and tantalum; theGroup VB metals, i.e., arsenic, antimony and bismuth; the Group VIAmetals, i.e., chromium, molybdenum and tungsten; the Group VIB metals,i.e., selenium, tellurium and polonium; the Group VIIA metals, i.e.,manganese, technetium and rhenium; and the Group VIII metals, i.e.,iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium andplatinum.

The preferred metal oxides and salts are those of the Group I metals,i.e., lithium, sodium, potassium and rubidium and copper, silver andgold; the Group II metals, i.e., strontium, calcium, barium, magnesiumand zinc, cadmium and mercury; the Group III metals, i.e., aluminum; theGroup IV metals, i.e., tin and lead and titanium and zirconium; theGroup V metals, i.e., vanadium and antimony; the Group VI metals, i.e.,chromium, molybdenium and tungsten; and the Group VIII metals, i.e.,iron and ruthenium, cobalt and nickel, platinum and palladium. The metalgroups referred to above correspond to the grouping of elements as setforth in the Revised Edition (1953) of the Periodic Chart of the Atoms(National Bureau of Standards), published by W. M. Welch PublishingCompany.

The preferred oxides and salts of ammonia, silicon and of theabove-described metals which are used to prepare the reaction productsof the present invention include the halides, i.e., the chlorides,bromides and fluorides and mixtures thereof, including halide hydrates,the acetate salts, the oxides and oxyhalides, nitrates and cyanates, thephosphates and sulfates, the carbonates, bromates, bromometalates, e.g.,bromoselenate, chromates, cyanides, ferrocyanides, fluoborates, iodates,nitrites and sulfites. Especially preferred anion moieties are halides,phosphates, carbonates, oxyhalides, halide hydrates, acetate, oxides,nitrates, cyanates, sulfates, chromates and bromates.

Specific ammonium and silicon salts and metal oxides and salts utilizedin accordance with this invention include ammonium acetate, ammoniumaluminum chloride, ammonium aluminum sulfate, ammonium bromate, ammoniumbromide, ammonium bromoplatinate, ammonium bromoselenate, ammoniumbromostannate, ammonium cadmium chloride, ammonium calcium arsenate,ammonium calcium phosphate, ammonium carbonate, ammonium chloride,ammonium chlorostannate, ammonium chromate, ammonium dichromate,ammonium cobalt sulfate, ammonium copper chloride, ammonium cyanate,ammonium cyanide, ammonium ferrocyanide, ammonium fluoborate, ammoniumiodate, ammonium triiodide, ammonium magnesium chloride, ammoniummolybdate, ammonium nickel chloride, ammonium metavanadate, ammoniumvanadium sulfate, ammonium zinc sulfate, actinium chloride, antimonytribromide, antimony trichloride, antimony pentachloride, antimonypentafluoride, antimony triiodide, antimony trioxide, antimonousoxychloride, antimonous dioxysulfate, antimony triselenide, antimonoussulfate, arsenic oxychloride, barium bromide, barium fluoride, bariumbromoplatinate, barium carbonate, barium chloride, barium fluoride,barium hypochloride, barium chromate, barium fluoride, barium iodate,barium iodide, barium nitrate, barium nitrite, barium oxide, bariumhypophosphate, barium tungstate, bismuth carbonate, cadmium acetate,cadmium bromide, cadmium carbonate, cadmium chloride, cadmiumchloroacetate, cadmium ferrocyanide, cadmium fluoride, cadmium iodide,cadmium nitrate, cadmium oxide, cadmium phosphate, calcium acetate,calcium aluminate, calcium bromide, calcium carbonate, calcium chloride,and the calcium chloride mono-, di- and tri-hydrates, calcium chromate,calcium fluoride, calcium iodide, calcium magnesium carbonate, calciumnitrate, calcium oxide, calcium sulfate, calcium sulfite, cesiumbromate, chromium acetate, chromous bromide, chromic bromide, chromouschloride, chromic chloride, chromous flouride, chromic fluoride,chromous iodide, chromic nitrate, chromous oxide, chromic sesquioxide,chromous sulfate, chromic sulfate, cobaltous acetate, cobaltous bromide,cobaltous chlorate, cobaltous chloride, cobaltic chloride, cobaltouschromate, cobaltous fluoride, cobaltic fluoride, cobaltous iodide,cobaltous nitrate, cobaltous oxide, cobaltic oxide, cobaltous sulfate,cuprice acetate, cupric bromide, cuprous bromide, cuprous carbonate,cuprous chloride, cupric chloride, cupric chromate, cuprous fluoride,cupric fluoride, cupric iodate, cuprous iodide, cupric nitrate, cuprousoxide, cupric oxide, cupric oxychloride, cuprous sulfate, cupricsulfate, cupric tungstate, aurous bromide, auric bromide, aurouschloride, auric chloride, aurous iodide, auric iodide, auric hydrogennitrate, ferrous acetate, ferric acetate, ferrous bromide, ferricbromide, ferrous carbonate, ferrous chloride, ferric chloride, ferrouschlorplatinate, ferrous fluoride, ferric fluoride, ferrous iodide,ferrous nitrate, ferric nitrate, ferrous oxide, ferric oxide, ferroussulfate, francium chloride, gallium ferrocyanide, germanium oxide,hafnium oxide, indium iodate, iridium sulfate, lanthanum carbonate, leadacetate, lead bromide, lead chloride, lead iodide, lead oxychloride,lead sulfate, lead sulfite, lithium acetate, lithium bromide, lithiumchloride, lithium fluoride, lithium iodide, lithium nitrate, magnesiumacetate, magnesium bromide, magnesium chloride, magnesium iodide,mangesium carbonate, magnesium nitrate, magnesium sulfate, manganeseacetate, manganese bromide, mercuric chloride, molybdenum dibromide,molybdenum tribromide, molybdenum tetrachloride, molybdenumpentachloride, molybdenum hexafluoride, molybdenum oxytrichloride,molybdenum metaphosphate, nickel acetate, nickel bromide, nickelchloride, nickel iodide, nickel carbonate, nickel nitrate, nickelsulfate, niobium pentafluoride, osmium sulfite, palladium bromide,palladium fluoride, palladium chloride, palladium iodide, palladiumnitrate, palladium sulfate dihydrate, platinum diiodide, platinumsulfate, polonium chloride, potassium acetate, potassium bromide,potassium chloride, potassium iodide, potassium cadmium iodide,potassium calcium fluoride, potassium carbonate, potassium molybdate,potassium nitrate, potassium nitrite, potassium rhodium sulfate,potassium sulfate, potassium tungstate, radium sulfate, rheniumoxytetrachloride, rhodium oxide, ruthenium sulfate, rubidium acetate,rubidium aluminum sulfate, rubidium bromide, rubidium tribromide,rubidium chloride, rubidium dichlorobromide, rubidium fluorodibromide,rubidium carbonate, rubidium copper sulate, rubidium fluoride, rubidiumnitrate, rubidium sulfate, scandium, sulfate, selenium oxide, disiliconhexachloride, silicon tetrafluoride, silicon tetraiodide, silicontetrachloride, silver bromide, silver carbonate, silver iodide, silvernitrate, silver phosphate, silver sulfate, sodium acetate, sodiumbromide, sodium chloride, sodium iodide, sodium carbonate, sodiumchloroiodide, sodium nitrite, sodium phosphate, sodium sulfate, stannousbromide, stannic bromide, stannous chloride, stannic chloride, stannousiodide, stannic iodide, stannous nitrate, stannic nitrate, stannoussulfate, strontium acetate, tantalum bromide, technetium chloride,tellurium iodide, titanium tetrachloride, titanium sulfate, tungstenhexafluoride, vanadium chloride, yttrium bromide, zinc acetate, zincdibromide, zinc dichloride, zinc diiodide, zinc nitrate, zinc phosphateand zirconium sulfate.

It is to be understood that mixtures of salts or mixtures or oxides andsalts may be used to prepare the reaction products of this invention.

Preferred salts include cobalt chloride tetrahydrate, cobalt chloridehexahydrate, cobalt acetate, cobalt chloride, cobalt sulfate, cadmiumacetate, cadmium ferrocyanide, cadmium chromate, cadmium phosphate,cadmium chloride, copper chloride, copper acetate, copper nitrate,calcium chloride, calcium oxide, calcium permanganate, nickel chloride,nickel acetate, nickel sulfide, iron oxide, iron chloride, silverchloride, silver acetate, silver nitrate, manganese chloride, tinchloride, lead chloride, lead iodide, sodium sulfate, barium chloride,barium bromide, aluminum chloride, aluminum acetate, ammonium chloride,antimony chloride, antimony oxychloride, antimony oxide, chromiumbromide, chromium sulfate, magnesium carbonate, magnesium bicarbonate,strontium chloride, molybdenum tetrachloride, lithium chloride,palladium dichloride, platinum tetrachloride, potassium bromide,rubidium monochloride, ruthenium dichloride, zinc oxide, silicontetrachloride and vanadium trichloride.

Phosphorus compounds containing trivalent phosphorus and characterizedby the absence of active protons and ionic halogens are essentialmaterials in the preparation of the reaction products of this invention.The phosphorus compounds containing trivalent phosphorus which areuseful in accordance with this invention are set forth in the following,commonly-assigned, U.S. Pat. Nos.: 3,014,910; 3,014,944; 3,014,945;3,014,946; 3,014,947; 3,014,948; 3,014,950; 3,014,951; 3,014,954;3,014,956; 3,029,271; 3,058,941 and 3,160,650, such patents being hereinincorporated by reference in order to fully set forth and disclose thetrivalent phosphorus-containing compounds which are utilized inaccordance with this invention. Thus, U.S. Pat. No. 3,014,910, entitled"Nitrogenous Organic Compounds of Phosphorus" and patented Dec. 26,1961, discloses phosphinyl phosphoramidites at column 1, lines 14through 39, column 2, lines 20 through 72, column 3, and column 4, lines1 through 70.

U.S. Pat. No. 3,014,944, entitled "Process of Preparing OrganicPhosphorus Compounds" and patented Dec. 26, 1961, discloses compoundshaving both trivalent phosphorus and pentavalent phosphorus estergroups. Such compounds are disclosed at column 1, lines 23 through 35,column 2, lines 9 through 65, column 12, lines 23 through 38, column 13,lines 5 through 30, column 13, lines 65 through 75, columns 14 through43 and Examples 1 through 104.

U.S. Pat. No. 3,014,945 is entitled "Triphosphinyl Phosphites" and waspatented on Dec. 26, 1961. It provides novel triphosphinyl phosphiteswhich are disclosed at column 1, lines 13 through 32 , column 2, lines10 through 72, columns 3 and 4, column 5, lines 1 through 37 andExamples 1 through 6.

U.S. Pat. No. 3,014,946 is entitled "Phosphinyl Diesters of AromaticPhosphates" and was patented Dec. 26, 1961. It discloses such aromaticphosphites at column 1, lines 15 through 44, column 2, lines 59 through71, columns 3 through 5, column 6, lines 1 through 18 and Examples 1through 3.

U.S. Pat. No. 3,014,947 is entitled "Phosphinyl Diesters ofPhosphonites" and was patented on Dec. 26, 1961. It discloses suchphosphonites at column 1, lines 13 through 32, column 2, lines 23through 72, column 3, column 4, lines 1 through 65 and Examples 1through 4.

U.S. Pat. No. 3,014,948 is entitled "Cyclic Esters of PhosphorusCompounds" and was patented on Dec. 26, 1961. It discloses cyclicphosphorus esters containing trivalent phosphorus at column 1, lines 14through 52, column 3, lines 61 through 75, columns 4 and 5, column 6,lines 1 through 34 and Examples 1 through 41.

U.S. Pat. No. 3,014,950 is entitled "Aromatic Di-Functional PhosphorusEsters" and was patented Dec. 26, 1961. It discloses di-functionalphosphorus esters containing trivalent phosphorus at column 1, lines 14through 40, column 3, lines 25 through 75, columns 4 and 5, column 6,lines 1 through 46 and Examples 1 through 5.

U.S. Pat No. 3,014,951 is entitled "Phosphite-Phosphonates" and waspatented Dec. 26, 1961. It discloses phosphite-phosphonates havingtrivalent phosphorus at column 1, lines 15 through 60, column 6, lines39 through 75, columns 7 through 10, column 11, lines 1 through 34 andExamples 1 through 43.

U.S. Pat. No. 3,014,954 is entitled "Polyphosphorus Esters and Method ofPreparing Same" and was patented December 26, 1961. It disclosespolyphosphorus esters containing trivalent phosphorus at column 1, lines17 through 72, columns 2 through 5, column 6, lines 1 through 50, column8, lines 58 through 75, column 9, lines 1 through 53, column 10, lines17 through 65, column 11, lines 65 through 75, column 12, lines 1through 23, column 13, lines 6 through 29 Examples 1 through 25.

U.S. Pat. No. 3,014,956 is entitled "Pentavalent Phosphorus Esters" andwas patented Dec. 26, 1961. The pentavalent phosphorus esters of thispatent are prepared by isomerization of trivalent phosphorus compoundsdisclosed at column 1, lines 53 through 72, column 2, lines 1 through 6,19, 26 through 35, 53, 60 through 63, column 5, lines 5 through 11, 23through 25, 31 through 36, 43 through 48, 56 through 60 and 69 through75, column 4, lines 8 through 17, lines 23 through 31 and 53 through 75,columns 5, lines 1 through 23, 35 through 75, column 6, column 7, lines1 and 2, 13 through 23, lines 28 through 67, column 8, lines 1 through5, lines 9 through 15, lines 21 through 28, lines 43 through 65, andlines 69 and 70, column 13, lines 65 through 73, column 15, lines 33through 75, column 16, column 17, lines 1 through 67, column 18, lines22 through 75, column 19, lines 70 through 75, column 20, lines 1through 31, column 21, lines 13 through 22, lines 54 through 61, lines66 through 72, column 22, lines 6 through 17 and Examples 1 through 25.

U.S. Pat. No. 3,029,271 is entitled "Organic Phosphorus Compounds" andwas patented Apr. 10, 1962. It discloses phosphorus compounds containingtrivalent phosphorus at column 1, lines 13 through 72, column 2, lines 3through 27, column 3, lines 15 through 40 and lines 64 through 75,column 4, lines 1 through 69 and Examples 1 through 12.

U.S. Pat. No. 3,160,650 is entitled "Process for Making 1-CyclohexenylPhosphonic Acid Diesters and an Intermediate Compound for Use Therein"and was patented Dec. 8, 1964. It discloses trivalent phosphoruscompounds at column 1, lines 40 through 67, column 2, lines 23 through72, column 3, lines 1 and 2, column 6, lines 20 through 75, column 7,lines 1 through 42 and Examples 1 through 10.

The preferred trivalent phosphorus-containing compound which is utilizedas a reactant in the process of the present invention is disclosed inU.S. Pat. No. 3,014,956, described above. In that patent, pentavalentphosphorus esters, i.e., phosphonates, are prepared by the isomerizationof phosphite-phosphonates. Although, as described in that patent,isomerization yields phosphonate esters in which no trivalent phosphorusis present, it has been found that if the isomerization or conversion isnot carried to completion, the final product is a mixture ofnon-isomerized phosphite-phosphonates and isomerized phosphonates. Thespecific portions of U.S. Pat. No. 3,014,956 which disclose thephosphite-phosphonates containing trivalent phosphorus have beenidentified above. Specific compounds which are preferred reactants inthe present invention, however, include: bis(2-chloroethyl) phosphite ofbis(2-chloroethyl)-1-hydroxy-ethylphosphonate

tris(2-chloropropyl) phosphite

triethylphosphite

alkyl diphenyl phosphite

bis(2-chloro-4-phenoxybutyl) methyl phosphite

trimethyl phosphite

triethyl phosphite

triallyl phosphite

triisopropyl phosphite

tri-n-propyl phosphite

tri-2-butenyl phosphite

tri-n-butyl phosphite

tri-tert-amyl phosphite

tri-n-hexyl phosphite

tri-n-heptyl phosphite

tris(2-ethylhexyl) phosphite

trioctenyl phosphite

tri-n-octyl phosphite

trinonyl phosphite

tridecyl phosphite

triundecyl phosphite

tri-tert-dodecyl phosphite

tridodecenyl phosphite amyldiethyl phosphite

butyl di-n-propyl phosphite

n-dodecyl dimethyl phosphite

ethyl octyl propyl phosphite

tris(2-chloroethyl) phosphite

tris(3-chloropropyl) phosphite

tris(2-chloropropyl) phosphite

tris(3,4-dichlorobutyl) phosphite

tris(2-chloro-4-pentenyl) phosphite

tris(2-bromoethyl) phosphite

tris(3-chloro-2-propenyl) phosphite

tris(3-iodylpropyl) phosphite

tris(2-chloroethyl) phosphite

tris(dichlorododecyl) phosphite

tris(2-ethoxyethyl) phosphite

2-chloroethyl diethyl phosphite

tris(2-phenoxypropyl) phosphite

3-bromopropyl bis(2-chloroethyl) phosphite

diamyl trichlorooctyl phosphite

2-chloroethyl phosphite

3-chloropropyl phosphite

4-chlorobutyl phosphite

2-chloroethyl methyl propyl phosphite

tris(2,3-dichloropropyl) phosphite

tris(2-bromo-3-chloropropyl) phosphite

tris(2-chloro-3-methoxypropyl) phosphite

tris(2-bromo-4-phenoxybutyl) phosphite

Instead of the above-described tribasic phosphites, there may beemployed certain phosphonites, i.e., diesters of hydrocarbyl orhalohydrocarbyl phosphonites, such as

dimethyl phenyl phosphonite

diethyl phenyl phosphonite

diethyl 2-propinyl phosphonite

ethylmethyl phenyl phosphonite

di-n-propyl methyl phosphonite

d-n-butyl benzyl phosphonite

bis(2-chloroethyl) p-tolyl phosphonite

bis(2-methoxyethyl) cyclohexyl phosphonite

diethyl n-propyl phosphonite

bis(2-bromo-3-ethoxypropyl) 2-bromo-ethyl phosphonite

diethyl 2-propinyl phosphonite

bis(2-butyloctyl) 2-butenyl phosphonite

di-n-hexyl p-biphenyl phosphonite

diundecyl n-hexyl phosphonite

bis(trichloropropyl) 2-methyl cyclopentyl phosphonite

diethyl 4-n-hexylamyl phosphonite

diallyl 2-phenylethyl phosphonite

dipentenyl 2-ethylhexyl phosphonite

bis(2-chloroethyl) phenyl phosphonite

bis(tetrachloropentyl) ethyl phosphonite

bis(3-bromopropyl) biphenylyl phosphonite

bis(2-chloroethyl) benzyl phosphonite

bis(2-bromo-3-chloropropyl) phenyl phosphonite

allyl propyl 2,4-dichlorophenyl phosphonite

bis(trichlrooctyl) cyclohexyl phosphonite

bis(4-fluorobutyl) 2-cyclohexenyl phosphonite

bis(4-chlorobutyl) ethyl phosphonite

bis(dichlorohexyl) phenyl phosphonite

bis(2-chloropropyl) n-butyl phosphonite

di-n-butyl pentachlorophenyl phosphonite

Alkyl and alkenyl dihydrocarbyl phosphinites are also useful inpreparing the reaction products of the present invention. Typicalphosphinites which may be used include the alkyl or alkenyldihydrocarbyl phosphinites such as ethyl, allyl, butyl, n-octyl, anddiethyl phenyl phosphinites or diphenyl or ditolyl phosphinite, benzylcyclohexyl phosphinite or diallyl phosphinite; the correspondinghaloalkyl esters such as 2-chloropropyl-di-p-tolyl phosphinite or2-fluoroethyl ethylmethyl phosphinite; the ether-substituted esters suchas 4-methoxybutyl or 3-phenoxy-2-chloropropyl di-n-butyl phosphinite ordi-β-naphthyl phosphinite; and the corresponding esters of thehalosubstituted phosphinic acids such as the methyl, pentyl, ethyl,2-butenyl, 2-chloroethyl, 3-methoxypropyl or 4-butoxy-2-bromo-pentylesters of bis(2-chloropropyl) phosphinite or of n-butyl (4-chlorophenyl)phosphinite.

A preferred phosphorus compound is a phosphonate/phosphite compounddisclosed in U.S. Pat. No. 3,014,956, described above. It has theformula ##STR1## wherein n has a value of from 0 to 4 and preferably hasa value of 1 or an average value of 2.

Equally preferred is the mixture of phosphorus compounds resulting fromthe incomplete conversion or isomerization of the compound of formula(I) to the phosphonate. The compound of formula (I) is converted to thephosphonate by the application of heat at about 190-200° C., for a shorttime, i.e. 1/4 to 2 hr. The phosphonate has the formula ##STR2## whereinn has a value of from 0 to 4 but preferably has a value of 1 or anaverage value of 2.

By controlling the time and temperature at which compound (I) is heated,a mixture is obtained which may vary from 99 percent compound (I) and 1percent compound (II) to 99 percent compound (II) and 1 percent compound(I). Best results are obtained by using compound (I) alone or by using amixture of compounds (I) and (II) wherein the mixture contains at least0.05 percent trivalent phosphorus and preferably from about 1 to about10 percent trivalent phosphorus.

The conditions under which the reaction of the phosphorus-containingcompound and the oxide or salt takes place are not critical. Thus, thephosphorus-containing compound and the oxide or salt are merely mixedtogether at ambient temperature and pressure. Under certain conditions,heating may be necessary to effect a more complete dissolution of theoxide or salt in the phosphorus-containing compound and thus insure amore complete and homogenous reaction.

The molar ratio of oxide or salt to total phosphorus compounds may befrom 1:1 to 1:20 or greater. Preferably, the ratio is from about 1:4 toabout 1:10.

The following, non-limiting examples will serve to illustrate thespecific embodiments of the reaction products of the present inventionand their preparation. In the examples, the percent of trivalentphosphorus present is determined by dividing the percentphosphite-phosphonate compound present by the number of phosphorus atomsin the phosphite-phosphonate compound. Thus, if there is 0.5 percentphosphite-phosphonate compound present, the number of phosphorus atomsin that compound would be 2 if n=0, 3 if n=1, 4 if n=2, 5 if n=3 and 6if n=4. Accordingly, if n=1, one would divide 0.5 percent by 3 todetermine the percent of trivalent phosphorus present.

EXAMPLE 1

A mixture of 63.8 g. of phosphonate (n=1) containing 0.5 percent ofphosphite-phosphonate and 26.7 g cobaltous chloride tetrahydrate isheated at 150° C., with stirring, for four hours. A creamy, dark bluelayer separates and is recovered, washed with toluene and dried for onehour at 170° C. The material is water-soluble and tacky.

EXAMPLE 2

A mixture of 126 g. of phosphonate (n=1) containing 1.0 percent ofphosphite-phosphonate and 28 g. of cadmium acetate is heated, withstirring, at 200° C. for two hours. Aliquots are taken at 15 minuteintervals. The viscosity of the aliquots is plotted versus time in FIG.1;

This example illustrates the great variety of products which areobtained in accordance with this invention. Complex reaction productsare obtained which range from liquids to glasses and from oil soluble towater soluble. Using the same reactants, a variety of products areobtained as a result of variation in reaction time.

EXAMPLE 3

A variety of products are prepared by reacting a phosphonate (n=1),containing 0.5 percent of phosphite-phosphonate, and the salts listedbelow. Thus, a reaction mixture containing 10 moles phosphonate and 1mole salt is heated at 150° C. for four hours to afford various coloredreaction products:

    ______________________________________                                        Salt             Color of Reaction Product                                    ______________________________________                                        CuCl.sub.2           green/black                                              CoCl.sub.2           blue                                                     CdCl.sub.2           water white                                              CaCl.sub.2           red                                                      NiCl.sub.2           blue/green                                               Cu(CO.sub.2 CH.sub.3).sub.2                                                                        yellow                                                   Co(CO.sub.2 CH.sub.3).sub.2                                                                        purple                                                   Ni(CO.sub.2 CH.sub.3).sub.2                                                                        blue                                                     Cd(CO.sub.2 CH.sub.3).sub.2                                                                        water white                                              ______________________________________                                    

EXAMPLE 4

Example 3 is repeated at a reaction temperature of 70° C. Results areidentical

EXAMPLE 5 ##STR3## , where n may vary from 0 to 4, but is preferably 1,is mixed with various metal oxides and salts at a 10:1 molar ratio. Themixtures are heated at 180° C. until solution occurs or a change inviscosity is noted, with a five minute heating limit. Results are setforth below:

    ______________________________________                                        Oxide or Salt                                                                             Color           Viscosity                                         ______________________________________                                        CaO         opaque, white   solid                                             ZnO         clear           very viscous                                      Cd(CO.sub.2 CH.sub.3).sub.2                                                               clear           high                                              Co(CO.sub.2 CH.sub.3).sub.2                                                               purple          glassy                                            Ni(CO.sub.2 CH.sub.3).sub.2                                                               clear, yellow-green                                                                           glassy                                            CuCl.sub.2  clear           glassy                                            NiCl.sub.2  yellow          glassy                                            AgCl        clear           medium increase                                   SnCl.sub.2  gray            glassy                                            HgCl.sub.2  gray, opaque    paste                                             PbCl.sub.2  clear           slight increase                                   Ag(CO.sub.2 CH.sub.3).sub.2                                                               red             slight increase                                   CoCl.sub.2  blue            medium increase                                   BaCl.sub.2  clear           gel                                               ______________________________________                                    

It is contemplated that similar reactions would occur using other oxidesand salts such as LiCl, Na₂ SO₄, KCl, MgCO₃, TiCl₄, ZrCl₄, VBr₃, CrBr,MoO₂, WC1₂, MnO₂, FeCl₃, PdI₂, PtF₅, AlPO₄, AuCl₃, RuCl₂, RbCl andSrCl₂.

EXAMPLE 6

Reaction products are prepared by heating the various inorganic saltslisted below, for 60 minutes, with a phosphonate of the formula:##STR4##

The phosphonate is prepared by incomplete isomerization of aphosphite-phosphonate of the formula: ##STR5##

The amount of trivalent phosphorus-containing phosphite-phosphonate inthe phosphonate is a function of the degree of completeness of theisomerization procedure.

The oxides and salts utilized are:

    __________________________________________________________________________    BaCl.sub.2                                                                              AlCl.sub.3                                                                              MgCO.sub.3                                                                              KBr                                             Cu(NO.sub.3).sub.2                                                                      Al(OH)(CO.sub.2 CH.sub.3).sub.2                                                         Mg(HCO.sub.2).sub.2 . H.sub.2 O                                                         RbCl                                            Cd.sub.2 Fe(CN).sub.6                                                                   NH.sub.4 Cl                                                                             MnCl.sub.2                                                                              RuCl.sub.2                                      CdCr.sub.2 O.sub.4 . 3H.sub.2 O                                                         SbCl.sub.3                                                                              MoCl.sub.4                                                                              SiCl.sub.4                                      Cd.sub.3 (PO.sub.4).sub.2                                                               SbOCl     Ni.sub.2 S                                                                              Ag.sub.3 (C.sub.6 H.sub.5 O.sub.7).sub.2        Ca(MnO.sub.4).sub.2 . 4H.sub.2 O                                                        Sb.sub.2 O.sub.3                                                                        PdCl.sub.2                                                                              Na.sub.2 SO.sub.4                               CrBr      AuCl.sub.3                                                                              PtCl.sub.4                                                                              SrCl.sub.2                                      Cr.sub.2 (SO.sub.4).sub.3                                                               BaBr.sub.2                                                                              AgCl      VCl.sub.3                                       Co.sub.2 (SO.sub.4).sub.3                                                               Fe.sub.2 O.sub.3                                                              PbI.sub.2                                                                     LiCl                                                                __________________________________________________________________________

Additional metal compounds which may be utilized are NaCl, TiCl₄, ZrCl₄,WCl₂, ZnO and HgCl₂.

The following, non-limiting examples illustrate embodiments of the flameretardant and smoke suppressant characteristics of the reaction productsof the present invention. It should be noted that, insofar as the effectof fire on humans, flame is far less dangerous, comparatively, thansmoke and noxious gases. By far the larger proportion of humans arekilled by smoke and gases than by flame of fires; accordingly, the smokesuppressant characteristics of the present reaction products areconsidered equally important, if not more important, than their flameretardant characteristics.

Further, it should be noted that flame retardance and smoke suppressionare antithetical characteristics. Due to the nature of flame and smokepropagation, increased flame indicates more complete combustion with asubsequent lowering of particulate matter and an increase in the ratioof the gas carbon dioxide to the significantly more lethal gas carbonmonoxide. When flame is suppressed, oxidation is less complete, toxicconcentrations of carbon monoxide quickly increase and visible smokeincreases. Lowering smoke concentrations without greatly increasingflame, is consequently, an outstanding technical achievement.

EXAMPLE 7

The reaction product of Example 1 is incorporated into plastisols of thefollowing formulations:

    ______________________________________                                        Ingredients          1       2       3                                        ______________________________________                                        Vinyl chloride/vinyl acetate (95:5)                                                                100     100     100                                      Dioctyl phthalate (DOP)                                                                             65      65      65                                      Example 1 reaction product                                                                          5       5      --                                       Ba/Cd stabilizer      1      --      --                                       Epoxidized soya oil   3      --      --                                       Phosphonate.sup.1    --      --       5                                       ______________________________________                                         .sup.1 Formula (II) where n = 1.                                         

The plastisols are fused on a metal hot plate. Formulations 1 and 2 arestable after one hour at 120° C. while formulation 3 discolors badly.

The reaction product of the invention imparts heat stability equivalentto a combination of standard heat stabilizers, i.e., Ba/Cd andepoxidized soya oil. Additionally, the reacton product apparentlyincreases the heat stability of the phosphonate.

EXAMPLE 8

Samples of the reaction product of Example 2, taken at 30, 60 and 120min., are incorporated, at 5 phr, in a 70 phr DOP/vinyl chloride-vinylacetate plastisol. No heat stabilizer is used. All samples are fused at185° C. for four minutes on a steel plate. None discolored and all arecompatible with the plastisol. A control, containing only 70 phrDOP/Opalon 440, discolored badly.

A horizontal burn test is run (15 sec, gas burner ignition) on 4×6"samples of the plastisol. Results are shown below:

    ______________________________________                                                            Time to Self-                                                                 Extinguishing                                             Sample              (Seconds)                                                 ______________________________________                                        30 min              19                                                        60 min              15                                                        120 min             18                                                        Control             75                                                        ______________________________________                                    

The horizontal burn test is described in paragraph S5of MVSS302 (MotorVehicle Safety Standard No. 302).

In accordance with that test, a material which stops burning within 60seconds of ignition meets governmental safety standards.

EXAMPLE 9

A mixture is prepared containing 22.8 g. SbCl₃ and 101.6 g. of a 60percent solution of a phosphite-phosphonate of the formula ##STR6## ;inethyl chloride. The mixture is stirred for one hour at 70° C. A clear,very stable solution is formed.

The solution is mixed into a standard polyvinyl chloride plastisolscreening formula containing 100 parts by weight PVC and 67 phr dioctylphthalate. The solution is added to the plastisol at a concentration ofone phr.

Film cast from the screening formula, containing 1 phr of the reactionproduct described above, is self-extinguishing within the test standardof the vertical burn test of Example 10.

EXAMPLE 10

A mixture of 92 g. antimony trichloride and 410 g. of thephosphite-phosphonate of Example 9 is stirred while heating at 100° C.for 1-1/2 hours.

A standard screening formula of 100 parts by weight polyvinyl chlorideand 67 phr dioctyl phthalate is prepared and to it is added one phr ofthe reaction product obtained above. A control sample is preparedcontaining only polyvinyl chloride and dioctyl phthalate.

During a 15 second ignition period, the control ignites and burnstotally during a vertical burn test. The sample containing 1 phr of theabove reaction product does not ignite.

Additionally, a cotton cloth is soaked with a 3 percent acetone solutionof the reaction product and dried for 15 min. at 70° C. The cloth is notignitable.

Vertical Burn Test Procedure

A specimen measuring one inch wide and 12 inches long is verticallymounted in a cabinet. The lower end of the specimen is exposed for 15seconds to a 1-1/2 inch flame from a 3/8 inch diameter barrel Bunsenburner supplied with natural gas. The specimen should not burn over amaximum of 90 seconds. Time of burning and inches burned are recorded.

EXAMPLE 11

The following flexible polyurethane foam formulations are prepared:

    ______________________________________                                                       Formulation                                                                   Weight (grams)                                                 Ingredients      1           2                                                ______________________________________                                        Polyol           100         100                                              Water            3.2         3.2                                              Triethylenediamine                                                                             0.45        0.45                                             Polymethyl siloxane                                                                            1           1                                                Stannous octoate 0.15        0.15                                             Toluene diisocyanate                                                                           48          48                                               Reaction product.sup.1                                                                         0           15                                               ______________________________________                                         .sup.1 Reaction product of 92 g. SbCl.sub.3 and 410 g. of                     phosphitephosphonate of Example 9.                                       

A sample of formulations 1 and 2 is subjected to ASTM 1692 which is themost widely used burning test for cellular plastics. In such test, aspecimen (6 inches×2 inches×1/2 inch) is supported on a horizontalhard-cloth support with the 1/2 inch dimension vertical.

One end is contacted for 60 seconds with a 1-1/2 inch high blue flamefrom a 3/8 inch diameter barrel Bunsen burner fitted with a 162-7/8 inchwide wingtop.

If the specimen instantly goes out, it is self-extinguishing. If thespecimen burns and subsequently goes out, it is characterized asself-extinguishing/burn rate given as inches and seconds burned. If thespecimen completely burns, its burn rate in inches/minute is given.

In the above test, Formulation 2 is self-extinguishing. Formulation 1, 6inches/10 seconds.

Similar results are attained using the reaction product of thephosphite-phosphonate of Example 9 and SbCl₃ in molar ratios of 1:1, 2:1and 4:1.

EXAMPLE 12

The following flexible polyurethane foam formulations are prepared:

    ______________________________________                                                     Formulation                                                                   Weight (grams)                                                   Ingredients    1         2         3                                          ______________________________________                                        Polyol         100.00    100.00    100.00                                     Triethylene diamine                                                                          0.65      0.65      0.65                                       Polymethyl siloxane                                                                          1.00      1.00      1.00                                       Water          3.20      3.20      3.20                                       Toluene diisocyanate                                                                         54.00     54.00     54.00                                      Stannous octoate                                                                             0.25      0.25      0.25                                       Reaction Product.sup.1                                                                       0.15      0.15      0.15                                       ______________________________________                                         .sup.1 Reaction product of SnCl.sub.2 and phosphitephosphonate of Example     9 in 1:1 molar ratio (Formulation 1), 3:5 molar ratio (Formulation 2) and     1:4 molar ratio (Formulation 3).                                         

All of the foams are self-extinguishing in accordance with the standardsof ASTM 1692.

Similar results are attained with a reaction product of CdCl₂ and thephosphite-phosphonate of Example 9.

EXAMPLE 13

Polyurethane foams are prepared from the following formulations:

                                      Example 13                                  __________________________________________________________________________               Formulation                                                                   Weight (grams)                                                     Ingredients                                                                              1   2   3   4   5  6    7                                          __________________________________________________________________________    Polyol     100.00                                                                            100.00                                                                            100.00                                                                            100.00                                                                            100.00                                                                            100.00                                                                            100.00                                     Triethylene diamine                                                                      0.65                                                                              0.65                                                                              0.65                                                                              0.65                                                                              0.65                                                                              0.65                                                                              0.65                                       Water      3.20                                                                              3.20                                                                              3.20                                                                              3.20                                                                              3.20                                                                              3.20                                                                              3.20                                       Polymethyl siloxane                                                                      1.00                                                                              1.00                                                                              1.00                                                                              1.00                                                                              1.00                                                                              1.00                                                                              1.00                                       Toluene diisocyanate                                                                     42.50                                                                             42.50                                                                             42.50                                                                             42.50                                                                             42.50                                                                             42.50                                                                             42.50                                      Stannous octoate                                                                         0.30                                                                              0.30                                                                              0.30                                                                              0.30                                                                              0.30                                                                              0.30                                                                              0.30                                       Reaction Product.sup.1                                                                   0.15                                                                              0.15                                                                              0.15                                                                              0.15                                                                              0.15                                                                              0.15                                                                              0.15                                       __________________________________________________________________________     .sup.1 Reaction Product 1 = CoCl.sub.2 + Phosphitephosphonate of Example      (1:2)                                                                         Reaction Product 2 = CoCl.sub.2 6H O + Phosphatephosphonate of Example 9      (1:2)                                                                         Reaction Product 3 = CdCl.sub.2 + Phosphitephosphonate of Example 9 (1:2)     Reaction Product 4 = NiCl.sub.2 + Phosphitephosphonate of Example 9 (1:4)     Reaction Product 5 = ZnCl.sub.2 + Phosphitephosphonate of Example 9 (1:2)     Reaction Product 6 = NiCl.sub.2 + Phosphitephosphonate of Example 9 (1:2)     Reaction Product 7 = SbCl.sub.3 +  Phosphitephosphonate of Example 9 (1:2     All foams are selfextinguishing according to ASTM 1692.                  

EXAMPLE 14

The foam formulation of Example 13 is repeated substituting 0.15 partsof the following reaction products:

1. SbCl₃ +Phosphonate of Example 6 (1:4)

2. SnCl₂ +Phosphonate of Example 6 (1:4)

3. SbCl₃ +Phosphonate of Example 6 (1:2)

4. CoCl₂ +Phosphite-phosphonate of Example 9 (1:2)

5. CdCl₂ +Phosphite-phosphonate of Example 9 (1:2)

6. NiCl₂ +Phosphite-phosphonate of Example 9 (1:4)

7. SbCl₃ +Phosphite-phosphonate of Example 9 (1:2)

The seven formulations are subjected to ASTM 1692 with the followingresults:

    ______________________________________                                                        Inches     Flame Out                                          Formulation     Burned     (Seconds)                                          ______________________________________                                        Control         Total       300+                                              1               1.5        11                                                 2               1.5        25                                                 3               3.0        17                                                 4               0.5        15                                                 5               2.5        40                                                 6               1.5        27                                                 7               3.0        35                                                 ______________________________________                                    

EXAMPLE 15

Vinyl foams are prepared from the following formulation:

    ______________________________________                                        Ingredients           Weight (grams)                                          ______________________________________                                        Vinyl chloride/vinyl acetate                                                  copolymer (95:5)      60                                                      Blending resin        40                                                      Phthalate blend plasticizer                                                                         40                                                      Dibasic lead phosphate                                                                               2                                                      Silicone prefoamer     4                                                      Reaction product.sup.1                                                                               5                                                      ______________________________________                                         .sup.1 1. SbCl.sub.3 + Phosphonate of Example                                 2. Cd(OAC).sub.2 + Phosphonate of Example                                     3. CdCl.sub.2 + Phosphonate of Example                                        4. SnCl.sub.2 + Phosphonate of Example 6                                      5. Ca(OAC).sub.2 + Phosphonate of Example                                     6. Control  no reaction product                                          

The formulations are subjected to flame spread and smoke generationtests.

The flame spread value is determined by observing the flame spread of anignited test panel in a calibrated two-foot flame tunnel as comparedwith a standard which is determined by observing the maximum flameadvance along the surface of preconditioned red oak and asbestos cementboard prior to evaluation of the test samples. Construction andcalibration of the flame tunnel and details concerning the flame spreadtest are given in the Journal of Paint Technology, Volume 39, No. 511,August, 1967. Read oak and asbestos have been assigned arbitrary flameratings of 100 and zero, respectively.

The smoke rating procedure is described in ASTM/E-84 and involves thestandardized burning of test samples using a photoelectric detectorattached to a recorder to plot the smoke evolution of the sample. Thedata recorded from the burning sampl are extrapolated via a linearrelationship to a standardized smoke generation curves for asbestoscement board and preconditioned red oak. Asbestos board and red oak havebeen assigned arbitrary smoke ratings of zero and 100, respectively, ormay also be described as the percent of light transmitted through thesmoke.

The results are tabulated below, wherein the smoke rating is the percentof light transmitted through the smoke.

    ______________________________________                                        Formulation Containing                                                                         Flame Rating Smoke                                           ______________________________________                                        Reaction Product 1                                                                             186          73                                              Reaction Product 2                                                                             102          75                                              Reaction Product 3                                                                              93          80                                              Reaction Product 4                                                                              97          84                                              Reaction Product 5                                                                              88          67                                              Control          104          64                                              ______________________________________                                    

The data show that the flame rating is equivalent to or better than thecontrol in every case except Reaction Product 1.

More importantly, the smoke rating is superior to the control in everycase. Reaction Products 3 and 4 are outstanding.

The efficacy of the reaction products of the invention as smokesuppressants without attendant loss of flame retardancy (with theexception of Reaction Product 1) is clearly shown.

EXAMPLE 16

The following formulation is prepared:

    ______________________________________                                        Ingredients          Parts (Weight)                                           ______________________________________                                        Polyol               100                                                      Toluene diisocyanate 54                                                       Triethylene diamine  0.65                                                     Water                4                                                        Polymethyl siloxane  1                                                        Stannous octoate     0.25                                                     Reaction product.sup.1                                                                             15                                                       ______________________________________                                         .sup.1 Reaction product 1 = Phosphitephosphonate of Example 9 + SbCl.sub.     (1:2 molar)                                                                   Reaction product 2 = Phosphitephosphonate of Example 9 + NiCl.sub.2 (1:2      molar)                                                                        Reaction product 3 = Phosphonate of Example 7 + SbCl.sub.3 (1:2               Reaction product 4 = Phosphonate of Example 7 + SbCl.sub.3 (1:10              Reaction product 5 = Phosphonate of Example 7 + CdCl.sub.2 (1:20              Reaction product 6 = Phosphonate of Example 7 + SnCl.sub.2 (1:20              Control = Phosphonate of Example 7                                       

The six formulations are subjected to ASTM 1692 and MVSS 302. ASTM 1692is a more stringent test since the wire mesh support used therein tendsto hold molten material, thus supplying fuel. The horizontal burning ofMVSS 302 allows burning material to fall away.

Heat stability at 140° C. is measured by:

(a) development of color and

(b) loss of physicals (i.e., crumbling of sample when compressed).

In the heat stability test, samples are placed in a circulating oven ata temperature of 140° C. Samples are tested at 30 minute intervals.

The results of ASTM 1692, MVSS 302 and heat stability tests aretabulated below:

    __________________________________________________________________________              Flame Retardancy       Heat Stability                               Sample Containing                                                                       Fresh       Aged 22 hrs at 140° C.                                                            (140° C.)                             __________________________________________________________________________    Reaction Product 1                                                                      4-6"/min - ASTM 1692                                                                      S.E. - ASTM 1692                                                                         >30 hrs.                                               S.E..sup.1 - MVSS 302                                                                     --         <40 hrs.                                     Reaction Product 2                                                                      4"/min - ASTM 1692                                                                        S.E. - ASTM 1692                                                                         >22 hrs.                                               S.E. - MVSS 302                                                                           --         <30 hrs.                                     Reaction Product 3                                                                      4-6"/min - ASTM 1692                                                                      S.E. - ASTM 1692                                                                          28 hrs.                                               S.E. - MVSS 302                                                                           --         --                                           Reaction Product 4                                                                      4"/min - ASTM 1692                                                                        S.E. - ASTM 1692                                                                          35 hrs.                                               S.E. - MVSS 302                                                                           --         --                                           Reaction Product 5                                                                      S.E. - ASTM 1692                                                                          S.E. - ASTM 1692                                                                         >64 hrs.                                               --          --                                                      Reaction Product 6                                                                      S.E. - ASTM 1692                                                                          S.E. - ASTM 1692                                                                          30 hrs.                                               --          --                                                      Control   10"/min - ASTM 1692                                                                       --          10 hrs.                                               --          --                                                      __________________________________________________________________________     .sup.1 S.E. = selfextinguishing                                          

EXAMPLE 17

Using the formulation of Example 16, comparative heat stability andflame retardance (ASTM 1692) of samples is determined, using thereaction product of CdCl₂ and the phosphonate of Example 6 andconventional flame retardant materials.

Results are shown in FIG. 2:

The preferred polymers utilized herein are plastisol and organosolformulations prepared from vinyl polymers. As is well known, plastisolsare fluent mixtures of particulate vinyl resins and high boiling organicplasticizers therefor which are substantially non-solvents for the vinylresin at ordinary temperatures, i.e., not over 35° C., but which arecapable of dissolving the resin at high temperatures, i.e., above 35° C.and, more commonly, form 120°-205° C. to form a fused thermoplasticfilm, sheet, layer or coating. Additionally, the vinyl plastisol may befoamed to provide an open or closed cell structure by expanding theplastisol and then heating to gel and fuse the expanded cellularstructure. Such foam is generally produced by one of three methods. Inthe compressed gas method, a gas, such as carbon dioxide or nitrogen, isdissolved in the plastisol under pressure. Upon release of the pressure,the dissolved gas expands in the plastisol to form the plastisol into aclosed cell vinyl sponge. A further process involves the use of chemicalblowing agents which decompose in the plastisol to release a gas, suchas nitrogen within the plastisol to form a foam or sponge structure. Afurther method for forming vinyl foam involves mechanical beating orfrothing of a plastisol to incorporate air therein. These methods canalso be used to prepare foams from other polymeric materials, such aspolyurethanes.

The materials which are flame retarded and smoke suppressed inaccordance with this invention include any of the conventional naturalor synthetic thermoplastic or thermosetting normally solid polymers usedfor industrial purposes. Preferably, the thermoplastic resin is apolymer of vinyl chloride or a self-blowing polymer such aspolyurethane. The vinyl chloride polymers can either be simple, unmixedhomopolymers of vinyl chloride or copolymers or terpolymers in which thesimple polymeric structure of polyvinyl chloride is interspersed atintervals with the residues of other ethylenically unsaturated compoundscopolymerizable therewith. The essential properties of the polymericstructure of polyvinyl chloride are retained if not more than about 40percent of a comonomer is copolymerized therewith. Suitable comonomersinclude vinyl halides such as vinyl bromide or vinyl fluorides; vinylesters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate andfatty acid vinyl esters; vinyl alkyl sulfonates; trichloroethylene;vinyl ethers such as vinyl ethyl ether, vinyl isopropyl ether and vinylchloroethyl ether; aromatic and cyclic unsaturated compounds such asstyrene, the mono- and polychlorostyrenes, coumarone, indene, vinylnaphthalene, vinyl pyridine, vinyl pyrrole; acrylic acid and itsderivatives such as ethyl acrylate, methyl methacrylate, ethylmethacrylate, ethyl chloroacrylate, acrylonitrile and methacrylonitrile,vinylidene compounds such as vinylidene chloride, vinylidene bromide,vinylidene fluorochloride; unsaturated hydrocarbons such as ethylene,propylene and isobutenes; allyl compounds such as allyl acetate, allylchloride and alyl ethyl ether; conjugated and cross-conjugatedethylenically unsaturated compounds such as butadiene, isoprene,chloroprene, 2,3-dimethyl butadiene-1,3-piperylene, divinyl ketone andesters such as diethyl maleate and diethyl fumarate.

Other exemplary thermoplastics are polyethylene, polybutylene,polypropylene, nylon, polycarbonates, polystyrene, polyvinylacetate,polyvinylidene chloride, polyacrylates.

An equally preferred group of polymers includes the rubbery polymers ofbutadiene and its homologs as well as copolymers and terpolymers ofbutadiene and its homologs with copolymerizable monomers. Illustrativecomonomers include vinyl armomatics, e.g., styrene, acrylic comonomers,e.g., acrylonitrile, methyl methacrylate and similar materials.Exemplary rubbery polymers which are included within the scope ofmaterials which are flame-retarded in accordance with this inventioninclude polysulfide rubber, polybutadiene, polyiosprene,polychloroprene, butyl rubber, nitrile rubber, propylene/ethylenerubber, styrene-butadiene rubber and similar materials.

The resins and cellulosic materials described above are used to makefilms, sheets, foams, carpet backing components and other articles ofmanufacture.

Thermosetting polymers or resins which may be flame retarded inaccordance with this invention include phenolic resins such asphenol-aldehydes, polyesters such as polyethylene terephthalate,polyadipates, polyazulates, urea formaldehyde resins, polyvinyl butyral,epoxies, polyamides and similar materials.

Natural polymers which are flame retarded in accordance with thisinvention include cellulose esters, e.g., cellulose acetate andcellulose nitrate, ethyl cellulose, cork and wood flour products, paper,cloth, cotton and similar cellulosic materials and natural rubber.

In the formulation of plastisol compositions of the present invention,the vinyl resin is uniformly dispersed in a mass of fluid plasticizer.The fluidity of plastisols is influenced in part by the particular resinselected, the plasticizer and the ratio of plasticizer to resin.Plastisols become less fluid as the ratio of plasticizer to resin isreduced. The viscosity of plastisol compositions can also be reduced bythe addition of small amounts of a diluent such as benzene, toluene,methyl ethyl ketone, petroleum solvents such as naphtha and similarmaterials. Plastisols which have been diluted by the addition of suchmaterials are known as "organosols" and are herein included in the term"plastisol". Plastisol compositions ordinarily contain from about 40 toabout 120 parts plasticizer per 100 parts resin, with about 60 to about100 parts plasticizer per 100 parts resin being particularly effectivefor foamable coatings.

The reaction products of this invention are conveniently added toplasticizers to impart flame retardant and smoke suppressantcharacteristics thereto. Typical plasticizers to which the reactionproducts of the invention may be added include phthalates, e.g., dioctylphthalate, dicyclohexyl phthalate, diundecyl phthalate, butyl benzylphthalate, phthalates prepared from mixtures of C₇, C₉ and C₁₁ alcohols,adipates, polymerics, e.g., oligoesters, petroleum oils, e.g.,naphthenic and paraffinic petroleum oils, natural oils, e.g., soya andlinseed oils and their epoxidized derivatives, trimellitates, aromaticextender oils and equivalent, conventionally used plasticizers.resorcinol dibenzoate, diphenyl phthalate, phenyl benzoate, o-tolylbenzoate, eugenol, guaiacol, and complexes of metals such as barium,cadmium, strontium, lead and tin. Suitable heat stabilizers includesulfides and sulfites of aluminum, silver, calcium, cadmium, magnesium,lead carbonate, lead sulfate, lead phthalate, barium oxide,barium-cadmium complexes and similar materials. Normally thecompositions contain about 0.5 to about 5 parts stabilizer per 100 partsresin.

When foamable compositions are desired, the plastisol utilized maycontain an effective amount of blowing agent. The larger the amount ofblowing agent, within practical limits, the greater is the expansion ofthe foam. About one-half to 10 parts of blowing agent per 100 partsresin is particularly effective for the production of foams of a densitywhich is most desirable as carpet and upholstery materials, althoughlarger amounts may be used. Foam densities of from about 12 to about 40pounds per cubic foot can be readily obtained. Of course, foams may beprepared by using compressed gas or by mechanically beating or frothing.Each method for producing a foam is particularly useful for specificaspects of industrial usage.

When a chemically blown foam is desired, the blowing agents which areused to provide the foam may be any of those blowing agents well knownand readily available to those skilled in the art. Thus, typical blowingagents include oxides, bicarbonates, substituted nitroso compounds,substituted hydrazides, acid azides and similar materials having anitrogen to nitrogen linkage which decomposes at elevated temperaturesto yield an inert gas high in nitrogen.

It is common practice to add accelerators to the plastisol compositionsto accelerate decomposition when chemical blowing agents are utilized.Typical accelerators include various metal salts such as dibasic leadphosphite, zinc laurate, zinc oxide, zinc stearate and cadmium octoate.These agents may also serve a dual function as stabilizers for theplastisol compositions.

Fillers are frequently employed to lower the cost of the finishedmaterial and to modify its properties. Typical fillers include calciumcarbonate and magnesium silicate. When fillers are employed in thecompositions they are generally present in an amount of up to about 150parts by weight of filler per 100 parts by weight of resin formulation.

Where a colored or tinted composition is desired, colorants orcolor-fast pigments are incorporated. The colorants or pigments willusually be present in an amount of about 1 to about 5 parts by weight to100 parts by weight of resin.

Surfactants, such as silicones, are normally added to form formulationsthat are to be mechanically frothed. The surfactants reduce the surfacetension of the foam and thereby increase the air or gas entrapmentcharacteristic of the foam.

Additionally, glass-forming inorganic materials such as zinc borate,zinc oxide, lead oxide, lead silicate and silicon dioxide may be addedto increase the flame retardant and smoke-generating characteristics ofthe foam.

While the invention has been described hereinabove with regard tocertain illustrative specific embodiments, it is not so limited sincemany modifications and variations are possible in the light of the aboveteachings. It is understood therefore that the invention may bepracticed otherwise than as specifically described without departingfrom the spirit and scope of the invention.

What is claimed is:
 1. A composition comprising a synthetic polymer anda reaction product of a phosphite/phosphonate of the formula ##STR7##wherein n has a value from 0 to 4 and a compound selected from salts andoxides of a metal selected from the group consisting of lithium, sodium,potassium, rubidium, magnesium, calcium, strontium, barium, titanium,chromium, zirconium, vanadium, molybdenum, tungsten, manganese, iron,ruthenium, nickel, palladium, platinum, cobalt, copper, silver, gold,zinc, cadmium, mercury, tin, lead, antimony, aluminum and mixturesthereof.
 2. A composition of claim 1 wherein said polymer is athermoplastic normally solid polymer.
 3. A composition of claim 2wherein said polymer is polyvinyl chloride, a polyurethane,polyethylene, polypropylene, polybutylene, a polyamide, a polycarbonate,polystyrene, polyvinylacetate, polyvinylidene chloride or apolyacrylate.
 4. A composition of claim 2 wherein said polymer ispolyvinyl chloride.
 5. A composition of claim 1 wherein said polymer isa thermosetting normally solid polymer.
 6. A composition of claim 5wherein said polymer is a phenolic resin, a polyester, a ureaformaldehyde resin, polyvinylbutyral, an epoxy resin or a polyamide. 7.A film or sheet containing a composition of claim 1.